Methods For Producing Higher Alcohols From Waste Plastic Pyrolysis Oil And The Higher Alcohols Obtained Therefrom

ABSTRACT

A method for producing a higher alcohol from a waste plastic feedstock is disclosed, comprising: (a) providing a hydrocarbon feed stream comprising a pyrolysis oil feed obtained from pyrolysis of plastic waste, wherein the pyrolysis oil comprises at least 20 wt % higher olefins with a carbon number in the range C5-C20, based on its total hydrocarbon content; (b) contacting the hydrocarbon feed stream with synthesis gas under hydroformylation conditions in the presence of a hydroformylation catalyst and recovering a hydroformylation product; (c) subjecting the hydroformylation product to hydrogenation and/or a distillation to recover a higher alcohol product.

FIELD

The present disclosure relates to methods for producing higher alcoholsfrom waste plastic pyrolysis oil and to the higher alcohols obtainedtherefrom.

BACKGROUND

The current environmental awareness, in particular the concerns overfossil fuel extraction and the increasing global problem of plasticwaste are driving the chemical industry to look for more sustainablefeeds and products. In line with these efforts, pyrolysis oil obtainedby pyrolysis of waste plastic can represent a viable alternative or avaluable addition to the conventional fossil fuel based feedstocks. Anadvantage of pyrolysis is that it can be used with mixed plastic waste,whereas conventional mechanical plastic recycling processes requiresextensive sorting and cleaning.

Although the liquid plastic pyrolysis products (pyrolysis oil) hasdesirable properties that recommends it as a feed for producing fuels,and C2=, C3= monomer for olefin based polymers, it is seldom in a formready to be used as a feedstock for higher alcohols. Often the pyrolysisoil has limited olefin content and/or contains high level ofcontaminants such as chlorides or metals.

U.S. Pat. No. 10,308,896 describes a rather cumbersome method forproducing oxo alcohols from waste plastic feedstock, which includespre-fractionating the feed stream comprising the waste plastic feedstockto produce a first heart cut paraffin stream, hydrotreating the firstheart cut paraffin stream and fractionating to obtain a second heart cutparaffin stream, followed by dehydrogenating of the second heart cutparaffin stream to form a stream comprising olefins, which is finallyhydroformylated to prepare oxo alcohols.

Accordingly, there is a need to provide improved methods for producinghigher alcohols from pyrolysis oil obtained from the pyrolysis of wasteplastic, wherein the pyrolysis oil can be used as the solely feed or incombination with conventional feedstocks.

SUMMARY

In a first aspect, the present disclosure provides a method forproducing a higher alcohol from a waste plastic feedstock, comprising:(a) providing a hydrocarbon feed stream comprising a pyrolysis oil feedobtained from pyrolysis of plastic waste, wherein the pyrolysis oilcomprises at least 20 wt % higher olefins with a carbon number in therange C5-C20, based on its total hydrocarbon content; (b) contacting thehydrocarbon feed stream with synthesis gas under hydroformylationconditions in the presence of a hydroformylation catalyst and recoveringa hydroformylation product; (c) subjecting the hydroformylation productto hydrogenation and/or a distillation to recover a higher alcoholproduct.

In embodiments of the disclosure the hydrocarbon feed stream may consistessentially of pyrolysis oil obtained from pyrolysis of plastic waste.

In other embodiments of the disclosure, the hydrocarbon feed stream mayfurther comprise a higher olefins conventional feed, wherein the higherolefins conventional feed can be a petroleum-based higher olefins feed,such as a higher olefins feed obtained by oligomerization of C3=, C4=,C5= olefins.

In embodiments of the disclosure the pyrolysis oil feed may comprise atleast 50 wt % linear alpha-olefins, more preferably at least 60 wt %linear alpha-olefins, based on its total olefin content. In suchembodiments, the pyrolysis oil feed may be characterized by an averagenumber of branches per molecule (also referred in the art as branchingindex) that is less than 1, preferably less than or equal to 0.8.

In embodiments of the disclosure the method may further comprise priorto step (b), subjecting the pyrolysis oil feed to a distillation therebyseparating one or more fractions corresponding to any narrow cut rangewithin the range C7-C20, in particular to the carbon number rangesC7-C19, C7-C10, C7-C12, C10-C13, C13-C17, C13-C15 and C16-C19.

Additionally or alternatively, the method may further comprise prior tostep (b) one or more of: subjecting at least a portion of thehydrocarbon feed stream, preferably the pyrolysis oil feed, to aselective reduction of diolefins in the presence of a nickel-containingcatalyst; contacting at least a portion of the hydrocarbon feed stream,preferably the pyrolysis oil feed, with a water solution to thereby atleast partially remove water-soluble contaminants; contacting at least aportion of the hydrocarbon feed stream, preferably the pyrolysis oilfeed, with one or more adsorbents suitable to thereby at least partiallyremove one or more contaminants selected from: water, metals, chlorides,nitrogen-containing compounds, oxygenates, and phosphorous-containingcompounds. In particular embodiments, the steps of contacting the atleast a portion of the hydrocarbon feed stream, preferably the pyrolysisoil feed, with a water solution and/or with one or more adsorbents areperformed prior to the selective reduction of diolefins.

In a further aspect, the present disclosure provides a higher alcoholobtainable by the method of the disclosure and compositions comprisingone or more derivatives of such higher alcohol.

The derivative may comprise esters of monocarboxylic acids, dicarboxylicacids, esters of polycarboxylic acids, alkoxylated alcohols, sulfatedalcohols, sulfated alkoxylated alcohols and alcohol ether amines.

Alternatively, the derivative may comprise esters of the primary alcoholcomposition with one or more acids. Further, the acids may comprise oneor more of phthalic acid, adipic acid, sebacic acid, lauric acid,myristic acid, palmitic acid, stearic acid, oleic acid, succinic acidand trimellitic acid.

BRIEF DESCRIPTION OF THE DRAWINGS

The following figures are included to illustrate certain aspects of thepresent disclosure and should not be viewed as exclusive embodiments.The subject matter disclosed is capable of considerable modifications,alterations, combinations, and equivalents in form and function, as willoccur to one having ordinary skill in the art and having the benefit ofthis disclosure.

FIG. 1 : Overall flow scheme for contaminants removal form waste plasticpyrolysis oil feed according to the invention.

FIG. 2 : Labelled GC-MS trace of low-boiling pyrolysis oil feed fractionaccording to the invention.

FIG. 3 : Area percentage bar chart for low-boiling pyrolysis oil feedfraction according to the invention.

FIG. 4 : Labelled GC-MS trace of high-boiling pyrolysis oil feedaccording to the invention.

FIG. 5 : Area percentage bar chart for high-boiling pyrolysis oil feedfraction according to the invention.

FIG. 6 : ¹H NMR spectrum of low-boiling pyrolysis oil feed fractionaccording to the invention. The insert shows the 4.5 to 8.0 ppm range;CDC13 was used as solvent indicated with (S) on the spectrum.

FIG. 7 : ¹³C{1H} NMR spectrum of low-boiling pyrolysis oil feed fractionaccording to the invention. CDC13 was used as solvent indicated with (S)on the spectrum.

FIG. 8 : ¹H NMR spectrum of high-boiling pyrolysis oil feed fractionaccording to the invention. The insert shows the 4.5 to 7.5 ppm range;CDC13 was used as solvent indicated with (S) on the spectrum.

FIG. 9 : ¹³C{1H} NMR spectrum of high-boiling pyrolysis oil feedfraction according to the invention. CDC13 was used as solvent indicatedwith (S) on the spectrum.

FIG. 10 : ¹H NMR spectrum of hydroformylated product of low-boilingpyrolysis oil feed fraction according to the invention. C6D6 was used assolvent. Grey rectangles indicate the residual diethyl ether from sodiumborohydride workup.

FIG. 11 : ¹³C{1H} NMR spectrum of hydroformylated product of low-boilingpyrolysis oil feed fraction according to the invention. C6D6 was used assolvent. Grey rectangles indicate the residual diethyl ether from sodiumborohydride workup. In the insert the range 55 to 80 ppm was expanded toshow the peaks attributed to: (1) primary alcohol (—CH2-OH); (2)secondary methyl branched alcohol (—CH(CH3)-OH); (3) secondary alkylbranched alcohol (—CH(R)—OH); (4) tertiary alcohol (—C(R)(R*)—OH)

FIG. 12 : ¹H NMR spectrum of hydroformylated product of high-boilingpyrolysis oil feed fraction according to the invention. C6D6 was used assolvent. Grey rectangles indicate the residual diethyl ether from sodiumborohydride workup. In the insert, the range 3.0 to 7.5 ppm wasexpanded.

FIG. 13 : ¹³C{1H} NMR spectrum of hydroformylated product ofhigh-boiling pyrolysis oil feed fraction according to the invention.C6D6 was used as solvent. Grey rectangles indicate the residual diethylether from sodium borohydride workup. In the insert the range 52 to 78ppm was expanded to show the peaks that correspond to: (1) primaryalcohol (—CH2-OH); (2) secondary methyl branched alcohol (—CH(CH3)-OH);(3) secondary alkyl branched alcohol (—CH(R)—OH).

DETAILED DESCRIPTION

Features and benefits of the present invention will become apparent fromthe following description, which includes examples intended to give abroad representation of the invention. Various modifications will beapparent to those skilled in the art from this description and frompractice of the invention. The scope is not intended to be limited tothe particular forms disclosed and the invention covers allmodifications, equivalents, and alternatives falling within the scope ofthe invention as defined by the claims.

The term “plastic” as used herein generally refers to a polymericmaterial (mainly polyethylene, polypropylene or their copolymers) madein whole, or part, of at least one organic monomer, that may contain oneor more modifications and/or may be compounded with one or moreadditives such as colorants, to form a useful material. Plastics includethermoset as well as thermoplastic polymeric materials. The term “wasteplastic” refers to a post-consumer plastic that is no longer needed forits intended purpose. Examples of waste plastic include emptied plasticcontainers, discarded plastic wrapping, and the like.

The term “hydrocarbon” refers to an organic compound consisting entirelyof hydrogen and carbon. Hydrocarbons include but are not limited toinclude paraffins, naphthenes, aromatics, and olefins.

The term “alkyl” refers to a hydrocarbyl group having no unsaturatedcarbon-carbon bonds. Optional heteroatom substitution or branching maybe present in an alkyl group, unless otherwise specified herein.

The term “linear alpha olefin (LAO)” refers to an alkenic hydrocarbonbearing a carbon-carbon double bond at a terminal (end) carbon atom ofthe main carbon chain. Most often, no side chain branches are present ina LAO, although there may occasionally be a minor amount of branchingcomponent in a given LAO sample.

The terms “branch,” “branched” and “branched hydrocarbon” refer to ahydrocarbon or hydrocarbyl group having a linear main carbon chain inwhich a hydrocarbyl side chain extends from the linear main carbonchain. The term “unbranched” refers to a straight-chain hydrocarbon orhydrocarbyl group without side chain groups extending therefrom.

Unless otherwise specified, the average branching number (averagebranching index) within a particular mixture of olefin oligomers equals(0×% linear olefins+1×% monobranched olefins+2×% dibranched olefins+3×%tribranched olefins)/100; wherein % linear olefins+% monobranchedolefins+% dibranched olefins+% tribranched olefins=100%. The foregoingare weight percentages (wt. %). For example, a mixture of C₈ olefinoligomers comprising 10% linear C₈ olefins, 30% monobranched C₈ olefins,50% dibranched C₈ olefins, and 10% tribranched C₈ olefins has an averagebranching index of 1.6. More highly branched individual olefin oligomers(e.g., tetrabranched and higher) may be weighted similarly to determinethe average branching index.

The present application provides methods for producing higher alcoholsfrom pyrolysis oil obtained by pyrolysis of waste plastic. The methodsdisclosed herein provide an alternative use for waste plastic, which mayotherwise end up in landfills or in the environment.

Pyrolysis Oil from Waste Plastic

The pyrolysis of waste plastic is well known in the art, and may involvea catalytic or non-catalytic process, in a continuous or a batchprocess. Examples of companies practicing waste plastic pyrolysisinclude Agilyx Corporation, Recycling Technologies Ltd, Plastic EnergyLtd., and Licella. Non-limiting examples of such processes are describedin patent applications WO2013/070801, WO2014/128430, and WO2011/123145,which are hereby incorporated by reference.

As mentioned above, the preparation of a pyrolysis oil from wasteplastic is well known in the art. Accordingly, the preparation of thepyrolysis oil is not necessarily part of the methods described herein.

However, in certain embodiments, the preparation of a pyrolysis oil fromwaste plastic may be a part of the method. In such embodiments, themethod comprises a step of preparing a pyrolysis oil from waste plastic.The preparation generally involves heating a container that has a wasteplastic therein so as to effect depolymerization of the waste plastic,and obtaining a pyrolysis oil or condensed (liquid) pyrolysis product.In such embodiments, the method described herein may be an integratedprocess comprising said preparation of the pyrolysis oil, wherein thepyrolysis oil is used without intermediate storage or transportationsteps.

An advantage of pyrolysis is that the process is not restricted tospecific plastic types. Accordingly, the waste plastic may comprise amixture of different types of plastic, and may still be used forpreparing the pyrolysis oil, without requiring sorting. Preferredplastic types are those including high density polyethylene, low densitypolyethylene, and propylene and their polyolefin copolymers. However,also other plastic types may be present, such as polyethyleneterephthalate (PET), polystyrene, and poly(vinyl chloride) (PVC).

Particularly polyolefins waste plastic is suited for pyrolysis and thepyrolysis oil obtained therefrom is suitable to be used as waste plasticfeedstock in the production of higher alcohols. The waste plasticfeedstock can be used as such, or blended with other higher olefinsfeedstock, such as conventional higher olefins feedstock obtained byoligomerization of olefins.

Depending on the origin and type of the waste plastic the pyrolysis oilobtained therefrom can be used as such or needs an additional clean-upto remove contaminants that may negatively impact the hydroformylationcatalyst, the hydroformylation process and/or the hydroformylationproduct quality requirements.

The pyrolysis oil includes typically one or more hydrocarbon materialsselected from paraffins, olefins, naphthenes, and aromatics. Therelative amount of these components may depend on the specific pyrolysisprocess conditions and the waste plastic material. The boiling range ofthe pyrolysis oil may depend on factors such as the pyrolysis conditionsand the plastic feed. Optionally, a waste plastic pyrolysis oil may befractionated in order to obtain a pyrolysis oil having a certain boilingrange and/or blended with a conventional higher olefins feed having acertain boiling range. The distillation points may be determined via gaschromatography according to ASTM D2887.

As used herein, conventional higher olefins are produced byoligomerization of any of propene, butenes, pentenes either as pure feedor as a mixture.

In the methods of the disclosure the conventional higher olefins feed tothe hydroformylation reaction is replaced or blended with the wasteplastic pyrolysis oil, such that the higher alcohols resulted from thehydroformylation reaction are either completely or partially made fromwaste plastic material.

Diolefin Hydrogenation

In embodiments of the disclosure, the waste plastic pyrolysis oil maycontain diolefins which can impact the hydroformylation catalystperformance. Typically, diolefins concentration can range from 0.1 to 20wt % based on the total olefin content.

Unless specified otherwise, the content of olefins, paraffins(n-paraffins and isoparaffins), naphthenes, and aromatics, may bedetermined using gas chromatography with vacuum ultraviolet absorptionspectroscopy detection according to ASTM D8071.

Depending on the impurities present in the pyrolysis oil, one or morefeed clean-up steps as described in the section “Contaminants Removal”may be performed before Diolefin Hydrogenation to protect thehydrogenation catalyst against deactivation.

A selective, low severity diolefins hydrogenation (DIOS) can beperformed to remove such diolefins. The hydrotreatment can be performedon the pyrolysis oil before or after blending it with the conventionalfeedstream.

The hydrotreatment step can be performed in a hydrotreatment unit asknown in the art. Hydrotreatment is generally done in the presence of acatalyst, under conditions suitable for the desired hydrogenation, asknown by the skilled person. Suitable catalysts and process conditionsare known in the art. Examples of suitable catalysts include catalystsbased on nickel, cobalt, and or molybdenum, such as Nickel (Ni),Nickel-Molybdenum (NiMo), and Cobalt-Molybdenum (CoMo) catalysts,preferably provided on a solid support such as alumina.

Methods for the selective hydrogenation of diolefins are known in theart. U.S. Pat. No. 3,696,160, hereby incorporated by reference,discloses the selective hydrogenation of diolefins into theircorresponding mono-olefins, using a sulfide nickel-tungsten catalyst.U.S. Pat. No. 6,118,034, hereby incorporated by reference, discloses theselective hydrogenation of diolefins at a temperature of 40° C. to 100°C., over a nickel-containing precipitated catalyst. U.S. Pat. No.6,469,223, hereby incorporated by reference, discloses the selectivehydrogenation of diolefins over a nickel-containing catalyst. Othercatalysts and/or process conditions than those described in U.S. Pat.Nos. 3,696,160, 6,118,034, and 6,469,223 may be used as well.

In particular embodiments, the low severity diolefins hydrogenationoperates at a high LHSV and low temperature (Table 1). The feed rate ofhydrogen was set at three times or more than the expected stoichiometricconsumption to manage heat release and catalyst deactivation. It wasfound that increasing the hydrogen feed rate may lead to a decrease inthe olefin yield, due to a percentage of olefins that are saturated toparaffins. The hydrogen feed rate was chosen such that diolefinsaturation has an acceptable impact on olefin yield. In a particularexample, between about 5 to about 13% olefins are saturated to paraffinsfor between about 60 to about 99% diolefin saturation in the DIOSreactor. The hydrogenation reactor has a diameter to height ratio ofless than one to capture pyrolysis oil particulates without appreciablepressure drop build-up. Optionally, the DIOS treatment can use one ormore of the following strategies to mitigate significant pressure drop:bypass tubes, modified scale baskets and bypass reactor.

TABLE 1 Diolefin Hydrogenation Operating Conditions and DIOS ReactorSettings Reactor Diolefin Saturation Guard Reactor UpstreamPretreatment: Oxygen Stripping Optional Catalyst NiMo + Inert/LowActivity Granding Layer Reactor Diameter to Height Ratio <1 BypassTubes/Modified Scale Baskets/ Yes Bypass Bed Average Reactor Temperature(° F.) 275 430 Heat Release, BTU/SCF H2 Consumed ~150  H₂ Treat Gas RateRelative to Stoichiometric  >3× H₂ Consumption, scf/bbl/scf/bbl LHSV,hr⁻¹ 3-6 Pressure, psig 310-370

Contaminants Removal

Waste plastic pyrolysis oil contains various contaminants such as metalsand heteroatom compounds. The term “heteroatom compounds” as used hereinrefers to molecules that include atomic species other than carbon andhydrogen. Examples of heteroatom compounds include compounds containingnitrogen, phosphor, oxygen, or halogens (such as chlorine and bromine).Such contamination can have a negative impact on the DIOS hydrogenationcatalyst and/or on the subsequent hydroformylation process andequipment. Moreover, the contaminants are also undesired in the higheralcohols obtained therefrom. The processes described herein not onlyallow for use of the waste plastic pyrolysis oil as feed in thehydroformylation process, but also allow for obtaining high-purityalcohols.

The waste plastic subjected to pyrolysis may comprise polyethyleneterephthalate (PET), high density polyethylene (HDPE), low densitypolyethylene (LDPE), polypropylene (PP) and various combinationsthereof. The type and the concentration of contaminants varies upon thesource of plastic waste. For example, waste plastic pyrolysis oilproduced from HDPE, LDPE and PP tend to have lower sulfur, oxygen andnitrogen content, while waste plastic pyrolysis oil produced from PETtend to have higher aromatic content. Other plastics, such as thepolyvinylchloride (PVC), may also be present in the waste plastic andtheir presence would require additional treatments to remove thechlorine. Plastic waste may contain other materials, such aspolyacrylonitrile, polyacrylic acid, polyvinyl sulfonate, which canintroduce also undesirable impurities (e.g., nitrogen, oxygen, sulfur).Contaminants can originate from multiple sources, including remnantsfrom additives added to the plastic to improve its properties, dirtaccumulating on the plastic during handling (use, collection,recycling), or unwanted polymers present in the waste plastic.

In the present methods, a broad-spectrum clean-up procedures able toremove or reduce to an acceptable level substantially all contaminantspresent in the waste plastic pyrolysis oil is applied. By applying theclean-up procedures, the contamination of one or more of the DIOShydrogenation catalyst, the hydroformylation catalyst and thehydroformylation product is reduced or avoided. One or more clean-upsteps of the waste plastic pyrolysis oil can be performed beforeintroducing the feedstock into the DIOS hydrogenation reactor.Alternatively or additionally, one or more clean-up steps are appliedafter the DIOS hydrogenation and before the hydroformylation process.

The overall flow scheme for contaminants removal (as shown in FIG. 1 )includes essentially two steps: i) a water wash wherein the pyrolysisoil feed (4) is contacted with water (3) in an extraction column/washtower (5) to remove all water-soluble contaminants, and ii) a series ofadsorbents (2), also referred to as a battery of adsorbents, which canbe composed of adsorbents with general functionality, such asnon-selective adsorbents and/or adsorbents with a specific functionalityused to remove a specific contaminant.

Further, the hydrocarbon-rich fraction may be transferred to a settler(6—optional) to remove residual water, and can be purified further via abattery of adsorbents. The battery of adsorbents is composed ofadsorbents with general functionality, such as non-selective adsorbentsand/or adsorbents with a specific functionality used to remove aspecific contaminant from the pyrolysis oil.

Each water-washing step is a liquid-liquid extraction process whereinthe pyrolysis oil is contacted with an aqueous solution in order toextract water-soluble impurities from the pyrolysis oil. The waterwashing may be done using an extraction column or water wash tower knownin the art. Examples of water wash towers or columns are described inpatent applications EP2338864 and WO93/13040, which are herebyincorporated by reference. Non-limiting examples of suitablecommercially available liquid-liquid extraction columns include KARR®columns and SCHEIBEL® columns, available from Koch Modular.

The water washing generally results in an aqueous phase (bottom stream)containing water-soluble components extracted from the pyrolysis oil,and an organic fraction (overhead stream) containing the hydrocarbonportion of the pyrolysis oil. The aqueous phase may be recirculated tobe contacted with further pyrolysis oil.

The aqueous solution generally comprises at least 50 wt % water,preferably at least 75 wt %, more preferably at least 95 wt %. Inparticular embodiments, the aqueous solution has an initial pH (i.e.prior to contacting with the pyrolysis oil) ranging between 6 and 8,preferably about 6.5 and 7.5, more preferably about 7. The aqueoussolution may be buffered to maintain a pH in such range.

In preferred embodiments, the relative volume of the pyrolysis oil feedto the volume of aqueous solution used in the one or more washing stepsranges from 1:1 to 1:200.

Additionally or alternatively, the pyrolysis oil is contacted with oneor more adsorbents which are suitable for removing one or morecontaminants such as (but not limited to): water, metals, chlorides,nitrogen-containing compounds, oxygenates, and phosphorous-containingcompounds. More particularly, the pyrolysis oil feed may pass over oneor more adsorbent beds, each containing one or more adsorbents. Each bedcan have different adsorbents, or multiple beds can have the sameadsorbent, depending on the adsorption capacity and the detected orexpected contaminant level. Depending on the specific contaminantspresent or expected to be present in the pyrolysis oil feed, one or moreadsorbents may be bypassed to avoid unnecessary purification steps. Inparticular embodiments, information regarding the contaminant level inthe feed may be obtained via in-line monitoring and analysis.

The methods described herein are not limited to specific adsorbents.Various adsorbents suitable for removing one or more contaminants areknown in the art and are commercially available. Examples of suitablemulti-purpose adsorbents include Zeolite 13X adsorbents, activatedcarbon, alumina, and clays. Non-limiting examples of suitable adsorbentsfor removing selected contaminants are provided below:

Water: silica gel adsorbents (e.g. Sylobead® silica gels available fromW. R. Grace) and molecular sieves (e.g. AZ-300, GB-620, Molsiv® ADG-401,and Molsiv® HPG-250 adsorbent available from UOP; and F-200 and 4Amolecular sieves available from BASF).

-   -   Nitrogen compounds: Axsorb® 911 adsorbent available from Axens.    -   Mercury: AxTrap™ 273 adsorbent available from Axens, Durasorb™        HG available from BASF, and Mersorb® available from Selective        Adsorption Associates Inc.    -   Chlorides: AxTrap™ 867 adsorbent available from Axens; UOP        CLR-204, UOP CLR-300, and UOP CLR-454 available from UOP;        Puraspec™ Clear™ chloride guards available from Johnson Matthey;        HTG-10 available from Haldor Topsoe; and BASF CL-850.    -   Silicon: ACT 971 and ACT 981 available from Axens.    -   Oxygenates: Axsorb® 911 adsorbent available from Axens; UOP        AZ-300, UOP GB-620, Molsiv® ADG-401, and Molsiv® HPG-250        available from UOP.    -   Sulfur: Axsorb® 913 adsorbent available from Axens; UOP ADS-120,        UOP ADS-130, UOP ADS-280, and UOP SG-731 available from UOP;        D-1275E, D1280E, and Prosorb® N available from BASF.    -   Phosphorus: TK-31 and TK-455 MultiTrap™ catalyst available from        Haldor Topsoe.

In particular embodiments of the disclosure, the entire pyrolysis oilfeed may be subjected to the washing step and/or contacting withadsorbents. In other embodiments, only a fraction (or a portion) of thepyrolysis oil feed may be subjected to such purification. In particularembodiments, the pyrolysis oil feed may be distilled as to obtainfractions having a different boiling range. The process may thencontinue with one or more fractions of interest. In other embodiments,the pyrolysis oil feed may be divided in fractions having the samecomposition, wherein some fractions may be purified and others not. Thefractions may be rejoined after the purification of one or more of thefractions. By setting the relative volume of the purified andnon-purified fractions, a targeted level of purification can be reached.

Hydroformylation

As used herein, hydroformylation, also referred to as the oxo process,represents the conversion of an olefin into an aldehyde throughmetal-catalyzed carbonyl addition. Hydroformylation reactions may takeplace by contacting synthesis gas (“syngas”), a mixture of carbonmonoxide (CO) and hydrogen (H₂), with an olefin in the presence of asuitable catalyst to form a hydroformylation reaction product.Frequently, the aldehydes within the hydroformylation reaction productare converted into alcohols through subsequent reduction, therebyforming primary alcohols having one carbon atom more than the olefinfrom which they were produced. Long-chain primary alcohols formedthrough hydroformylation and subsequent reduction may find many usesincluding, for example, organic solvents, detergents, surfactants, orthe alcohol component of ester-based plasticizers for polymers (e.g.,PVC).

Typical hydroformylation catalysts comprise a Group 9 transition metal,such as cobalt or rhodium. Examples of suitable hydroformylationcatalysts comprising cobalt include cobalt carbonyls, such as Co₂(CO)₈,which may convert to hydridocobalt tetracarbonyl HCo(CO)₄ under highCO/H₂ pressures commonly encountered during hydroformylation. Suitablesyngas pressures effective for forming HCo(CO)₄ in situ may range fromabout 1 MPa to about 30 MPa, with a ratio of H₂:CO partial pressuresranging from about 2:3 to about 3:2, preferably about 1.2:1. Suitablereaction temperatures during hydroformylation may range from about roomtemperature to about 200° C. (i.e., about 25° C. to about 200° C.), orany subrange in between.

In embodiments of the disclosure higher alcohols are produced with ahigh pressure cobalt catalyzed oxo process. The cobalt is fed togetherwith the olefin feed and syngas to the Oxo reactors at a pressure ofabout 280-300 bar and a temperature of about 160-200° C. At theseconditions the olefins are hydroformylated to aldehydes and someby-products such as acetals and dimers. The hydroformylation product ishydrogenated over a copper chromite, sulfided NiMo or sulfided CoMocatalyst. Typical process conditions include a temperature range between80-200° C. and a pressure of 60 to 150 bar. After hydrogenation theproduct is distilled to remove any unreacted olefins, paraffins,aromatics and naphthenics (if present), and to recover the alcoholfraction. After distillation a final mild hydrogenation may be requiredto remove traces of aldehydes. Depending on the boiling point range ofthe olefins present in the hydroformylation feed, a range of higheralcohols products is obtained.

Alternatively the hydroformylation reaction is run on a low pressureRh-catalyst process employing process conditions known in the art.Examples of Rh-catalyst hydroformylation process are described forexample in patent number EP 1004563 B1 and in patent applicationpublication number WO 2017/080690 A1.

The methods of the invention describe producing higher alcohol from ahydrocarbon stream consisting essentially of pyrolysis oil feed obtainedfrom plastic waste or from a blend of a waste plastic pyrolysis oil feedwith a conventional feed. In embodiments of the invention, the pyrolysisoil feed comprises at least 20 wt % higher olefins with a carbon numberin the range C5-C20, based on its total hydrocarbon content.Advantageously, by providing a pyrolysis oil feed that comprises atleast 20 wt % higher olefins one can avoid dilution with large amountsof non-reactive molecules which would require more reactor anddistillation capacity to produce and recover alcohols.

In embodiments of the invention, the pyrolysis oil obtained from wasteplastic contains an increased level of linear alpha olefins, as comparedto the conventional petroleum-based feedstock. The pyrolysis oilcontained at least 10 wt % linear alpha olefins, in further embodimentsat least 50 wt % linear alpha olefins based on their total olefincontent. In embodiments of the invention, the olefins comprised in thepyrolysis oil are characterized by an average branching number permolecule lower than 1, preferably lower than 0.8. Olefin oligomershaving an average branching number of about 2.2 or less may exhibitadvantageous biodegradation properties. Advantageously, the higheralcohols produced therefrom are characterized by also by a low averagebranching number, such as an average branching number per molecule lowerthan 2, which may confer an improved biodegradability to the derivativesproduced from such alcohols.

In embodiments of the invention, the hydrocarbon feed stream consistessentially of the pyrolysis oil.

In further embodiments of the invention the hydrocarbon feed streamcomprises further a conventional feed stream. Blending a conventionalhigher olefin feed with the pyrolysis oil allows tailoring the averagebranching number per molecule of the hydrocarbon feed.

In yet other embodiments using relatively low concentrations ofpyrolysis oil (for example as low as about 1 wt % or even lower) allowsfor lowering the concentration of certain contaminants in thehydrocarbon feed via dilution, thereby reducing the adverse effects ofsuch contaminants on other process steps such hydroformylation. Whenusing very low pyrolysis oil concentrations in the hydrocarbon feedstream, in particular concentrations below 1 wt %, the contaminants maybe diluted to such extent, that no further treatments of the hydrocarbonfeed stream are necessary.

By using a waste plastic pyrolysis feedstock source alone or by blendingthe waste plastic pyrolysis feedstock source with a conventionalpetroleum-based feedstock, the throughput of the oxo alcohol plant canbe increased, thereby improving the efficiency of the process.

To facilitate a better understanding of the present disclosure, thefollowing examples of preferred or representative embodiments are given.In no way should the following examples be read to limit, or to define,the scope of the invention.

Experimental Procedures

Standard air-sensitive technique and purification methods were utilizedfor these tests. Commercially sourced materials were utilized asreceived or purified according to standard procedures (Anarego, W. L.;Chair, C. L. Purification of Laboratory Chemicals; 5 ed.; Elsevier:Oxford, 2003).

The Co₂(CO)₈ pre-catalyst was purchased from Strem Chemicals(Newburyport, MA) and stored at −35° C. prior to use. Unless otherwisenoted, manipulations were conducted at ambient temperature (22-28° C.).

To characterize the pyrolysis oil compositions and the alcoholcompositions of the present invention, gas chromatographic (GC) andnuclear magnetic resonance (NMR) methods were employed. Two NMR methodswere employed to characterize the branching in the alcohol samples: ¹HNMR to determine the average number of branches per molecule and ¹³C NMRto determine the branch site distribution,

GC-MS data were obtained on an Agilent 5977 Series GC/MSD system. Dataanalysis was performed using vendor provided MassHunter GC/MSacquisition software in conjunction with MSD ChemStation and the NISTMass Spectra Search Program (v2.2; June 2014). Further analyses werecarried out with OrinPro2019 and Microsoft Excel.

¹H and ¹³C NMR spectroscopic data were collected on a 400 MHz Bruker NEONMR spectrometer. ¹H and ¹³C{1H} chemical shifts are reported in ppmrelative to SiMe4 (¹H and ¹³C{1H} δ=0.0 ppm) using the known chemicalshift of residual proton or carbon resonances, respectively,corresponding to deuterated solvents (i.e., C₆D₆, CDCl₃ etc.) asreported in J. Am. Chem. Soc., (2010), v. 29, pp. 2176-2179.

Pyrolysis Oil Feed Characterization

The pyrolysis oil feed was derived from polyethylene plastic subjectedto pyrolysis and distillation to afford broad distillate cuts. The wasteplastic pyrolysis oil feed was clear with a very pale yellow color. Thepyrolysis oil feed was characterized by GC-MS (FIG. 2-5 ) and NMRspectroscopy (FIGS. 6-9 ).

Major components of the mixtures are outlined in Table 2 (low-boilingcut) and Table 3 (high-boiling cut). Total linear alpha olefin contentmeasured for the low-boiling cut was about 73 wt %. Total linear alphaolefin content measured for the high-boiling cut was about 64 wt %.Consistent with GC-MS results, NMR spectroscopy (¹H and ¹³C{1H})confirmed that the feeds were predominantly (i.e. more than 50 wt %)comprised of vinyl-terminated olefins.

As shown in FIGS. 6-9 , NMR data indicate the presence of a substantialnumber of trace components including but not limited to aromatics anddienes.

In the low-boiling cut (93-177° C.) toluene and trace xylenes wereidentified. The ¹³C NMR spectroscopic shifts centered at 39.55 ppm (FIG.7 ) in conjunction with ¹H NMR spectroscopic shifts centered between6.61-6.08 ppm (FIG. 6 ) are consistent with the presence ofnon-conjugated (“step-dienes”), such as 1,4-hexadiene. The presence ofthese species is a potential concern as they are easily isomerized underhydroformylation conditions to afford conjugated dienes that are knowncatalyst poisons.

TABLE 2 Major Components Identified by GC-MS for low-boiling cut:Low-Boiling Cut 93° C.-177° C. Area % Total LAO Content 73.24 1-hexene2.51% 1-heptene 6.93% 1-octene 12.89% 1-nonene 16.09% 1-decene 21.13%1-undecene 7.77% 1-dodecene 3.74% 1-tridecene 2.17% Other Components26.76 toluene 5.29% octane 4.16% 2,4-dimethyl-1-heptene 3.21%1,8-nonadiene 3.22% nonane 4.05% 1,9-decadiene 3.40% decane 3.44%

TABLE 3 Major Components Identified by GC-MS for high-boiling cut: HighBoiling Cut 177° C.-232° C. Area % Total LAO Content 63.78 1-nonene1.02% 1-decene 9.54% 1-undecene 16.53% 1-dodecene 14.16% 1-tridecene11.52% 1-tetradecene 8.44% 1-pentadecene 2.56% Other Components 36.22%1,9-decadiene 1.42% decane 2.08% 1,10-undecadiene 3.82% undecane 4.10%1,11-dodecadiene 4.89% dodecane 4.43% 1,12-tridecadiene 5.09% tridecane3.18% 1,13-tetradecadiene 3.54% tetradecane 2.31% 1,14-pentadecadiene2.56%

Pyrolysis Oil Feed Hydroformylation

A high-pressure, 316 SS, continuously-stirred, constant pressure batchautoclave reactor (600 mL) equipped with supervisory control and dataacquisition capabilities was utilized for waste plastic pyrolysis oilfeed hydroformylation.

The interior of the reactor was fitted with a glass liner. In a nitrogenfilled glovebox, solvent, the plastic waste feed and pre-catalyst wereintroduced into the reactor in the volumes and quantities specified inTable 4. The reactor was then sealed under nitrogen (3 psig N₂), removedfrom glovebox and connected to a reactor system with supervisorycontrol, heating, stirring, cooling and process gas-supply. The reactorsystem was then pressurized to 1500 psig (H₂/CO) at room-temperature(23° C.) and then heated to 150° C. The reactor reached processtemperature in about 20 min. Once at process temperature, the batchautoclave was operated in constant pressure mode for 4 h. At the end ofthe run, the process gas supply (syngas) was halted and the unitde-pressurized and purged with nitrogen. Once cool, the reactor wasopened and the liquid hydrocarbon product was filtered through a columnof activated, basic alumina to remove catalyst ash.

TABLE 4 Hydroformylation Conditions: Entry 1 2 Experiment # Low BoilingCut High Boiling Cut Pre-Catalyst CO₂(CO)₈ CO₂(CO)₈ Pre-Catalyst MW341.95 341.95 Catalyst Concentration in reactor 20.00 20.00 (mM)Catalyst Concentration in reactor 1597.37 1561.06 (PPM; mg[Co]/KgOlefin) Pre-catalyst quantity (mmol) 0.900 0.900 Pre-catalyst mass (mg)307.755 307.755 Syngas (1:1) Pressure 1500 1500 Run Temperature ° C. 150150 Run Time (h) 4 4 Feed mass (g) 66.41 67.95 Feed volume (mL) 90.0090.00 Feed Density (g/mL) 0.74 0.76 Solvent None None Total liquidvolume (mL) 90 90

NaBH₄ Finishing

The crude alcohol from each hydroformylation reaction was transferredinto a round-bottom flask (500 mL) equipped with PTFE-coated magneticstir bar. Under a nitrogen atmosphere, a slight excess of NaBH₄ (about17.5 g) was added. The material was allowed to stir 16 hours. Theresulting slurry was then combined with pentane (100 mL). Each reactionmixture was then transferred to a larger beaker (1 L) and water wasslowly added over the course of 1 hour. The reaction mixture was thenneutralized to a pH of about 6.5 by addition of 10% HCl/H₂O. Onceeffervesce ceased upon addition of HCl, each reaction mixture wassubjected to an aqueous work-up, wherein Et2O (3×150 mL) was used toextract the product into an organic phase. The organic phases werecombined, dried with MgSO₄ and filtered. The resulting colorlessfiltrates were concentrated under rotary evaporation to remove volatiles(principally pentane).

The crude alcohol product was analyzed by ¹H and ¹³C{1H} NMRspectroscopy as shown in FIGS. 10-13 . Yield and conversion estimatesare shown in Table 5.

In both instances, ¹H NMR spectroscopic signals consistent with alcoholformation were present. This was verified by ¹³C NMR spectroscopy wherediagnostic chemical shifts, located between 62-75 ppm, were present andconsistent with the formation of primary, secondary and tertiaryalcohols. FIGS. 11 and 13 show in the insert the peaks that wereassigned to: (1) primary alcohol (—CH2-OH); (2) secondary methylbranched alcohol (—CH(CH3)-OH); (3) secondary alkyl branched alcohol(—CH(R)—OH); (4) tertiary alcohol (—C(R)(R*)—OH).

TABLE 5 Alcohol Yield and Conversion Isolated Product YieldHydroformylated Low Boiling Cut: 19.95 g crude liquid product; 30.4%Hydroformylated High Boiling Cut: 53.20 g crude liquid product; 78.3%Estimated Conversion Hydroformylated Low Boiling Cut: (0.83/4.83)*100 =17.2% Hydroformylated High Boiling Cut: (26.45/30.45)*100 = 86.9%

Conversion is expressed as the percent relative intensity of alcoholcontent vs. residual unsaturation content. The integration range forolefin unsaturation includes vinyl, vinylidene and internalunsaturations. The integration range for alcohols captures the intensityof protons located alpha to the —OH functional group.

Integrated range for olefinic unsaturation corresponds to 4.8-5.8 ppm(C6D6). Integrated range for estimated alcohol content corresponds to3.35-4.0 ppm (C6D6).

The following formula was used for the Estimated Conversion (%Conversion) as a function of the Integrated Alcohol Intensity (IAI) andIntegrated Unsaturated Intensity (IUI):

${\%{Conversion}} = {\frac{({IAI})}{({IUI}) + ({IAI})} \times 100}$

Hydrogenation

Alternatively or in combination with sodium borohydride reduction, thehydroformylation product may be hydrogenated to convert residual olefincontent to paraffinic materials. Typically, this is conducted byallowing the neat hydroformylation product or a solution thereof tocontact a hydrogenation catalyst containing one or more of the followingtransition metals Pd, Pt, Co, Ni, or Mo in the presence of hydrogen gas.Preferably these reactions are conducted with a hydrogen pressure above100 psig at a temperature higher than 50° C.

Distillation

The crude hydroformylation product or product mixture obtained fromeither or both hydrogenation and/or sodium borohydride reduction can be,optionally, distilled. The purpose of distillation is to separateproduct alcohols and other molecules in the product mixture(s) byboiling point. The distillation technique may proceed at atmosphericpressures or reduced pressures and may utilize low-resolutiondistillation techniques (i.e., short-path) or high-resolutiondistillation techniques (i.e., distillation towers, spinning-bandcolumns etc.).

Additional Embodiments

This disclosure may further include one or more of the followingnon-limiting embodiments:

E1. A method for producing a higher alcohol from a waste plasticfeedstock, comprising: (a) providing a hydrocarbon feed streamcomprising a pyrolysis oil feed obtained from pyrolysis of plasticwaste, wherein the pyrolysis oil comprises at least 20 wt % higherolefins with a carbon number in the range C5-C20, based on its totalhydrocarbon content; (b) contacting the hydrocarbon feed stream withsynthesis gas under hydroformylation conditions in the presence of ahydroformylation catalyst and recovering a hydroformylation product; (c)subjecting the hydroformylation product to hydrogenation and/or adistillation to recover a higher alcohol product.

E2. The method of embodiment E1, wherein the hydrocarbon feed streamconsists essentially of pyrolysis oil obtained from pyrolysis of plasticwaste.

E3. The method of embodiment E1, wherein the hydrocarbon feed streamfurther comprises a higher olefins conventional feed.

E4. The method of embodiment E3, wherein the higher olefins conventionalfeed is a petroleum-based higher olefins feed, such as a higher olefinsfeed obtained by oligomerization of C3=, C4=, C5=olefins.

E5. The method of any one of embodiments E1-E4, wherein the pyrolysisoil feed comprise at least 50 wt % linear alpha-olefins, more preferablyat least 60 wt % linear alpha-olefins, based on its total olefincontent.

E6. The method of embodiment E5, wherein the pyrolysis oil feed ischaracterized by an average number of branches per molecule that is lessthan 1, preferably less than or equal to 0.8.

E7. The method of any one of embodiments E1-E6, further comprising:prior to step (b), subjecting the pyrolysis oil feed to a distillationthereby separating one or more of fractions corresponding to any narrowcut range within the range C7-C20, in particular to the carbon numberranges C7-C19, C7-C10, C7-C12, C10-C13, C13-C17, C13-C15 and C16-C19.

E8. The method of any one of embodiments E1-E7, further comprising:prior to step (b), subjecting at least a portion of the hydrocarbon feedstream, preferably the pyrolysis oil feed, to a selective reduction ofdiolefins in the presence of a nickel-containing catalyst.

E9. The method of any one of embodiments E1-E8, further comprising:prior to step (b), contacting at least a portion of the hydrocarbon feedstream, preferably the pyrolysis oil feed, with a water solution tothereby at least partially remove water-soluble contaminants.

E10. The method of any one of embodiments E1-E9, further comprising:prior to step (b), contacting at least a portion of the hydrocarbon feedstream, preferably the pyrolysis oil feed, with one or more adsorbentssuitable to thereby at least partially remove one or more contaminantsselected from: water, metals, chlorides, nitrogen-containing compounds,oxygenates, and phosphorous-containing compounds.

E11. A higher alcohol obtainable by the method of any one of embodimentsE1-E10.

E12. A composition comprising one or more derivatives of the higheralcohol of embodiment E11.

E13. The composition of embodiment E12, wherein the derivative comprisesesters of monocarboxylic acids, esters of dicarboxylic acids, esters ofpolycarboxylic acids, alkoxylated alcohols, sulfated alcohols, sulfatedalkoxylated alcohols and alcohol ether amines.

E14. The composition of embodiment E12, wherein the derivative comprisesesters of the primary alcohol composition with one or more acids.

E15. The composition of embodiment E14, wherein the acids comprise oneor more of phthalic acid, adipic acid, sebacic acid, lauric acid,myristic acid, palmitic acid, stearic acid, oleic acid, succinic acidand trimellitic acid.

The disclosure herein suitably may be practiced in the absence of anyelement that is not specifically disclosed herein and/or any optionalelement disclosed herein. While compositions and methods are describedin terms of “comprising,” “containing,” or “including” variouscomponents or steps, the compositions and methods can also “consistessentially of” or “consist of” the various components and steps. Allnumbers and ranges disclosed above may vary by some amount. Whenever anumerical range with a lower limit and an upper limit is disclosed, anynumber and any included range falling within the range is specificallydisclosed. In particular, every range of values (of the form, “fromabout a to about b,” or, equivalently, “from approximately a to b,” or,equivalently, “from approximately a-b”) disclosed herein is to beunderstood to set forth every number and range encompassed within thebroader range of values. All numerical values within the detaileddescription and the claims herein are modified by “about” or“approximately” with respect to the indicated value, and take intoaccount experimental error and variations that would be expected by aperson having ordinary skill in the art. Also, the terms in the claimshave their plain, ordinary meaning unless otherwise explicitly andclearly defined by the patentee. Moreover, the indefinite articles “a”or “an,” as used in the claims, are defined herein to mean one or morethan one of the element that it introduces.

Unless otherwise indicated, all numbers expressing quantities ofingredients, properties such as molecular weight, reaction conditions,and so forth used in the present specification and associated claims areto be understood as being modified in all instances by the term “about.”Accordingly, unless indicated to the contrary, the numerical parametersset forth in the following specification and attached claims areapproximations that may vary depending upon the desired propertiessought to be obtained by the embodiments of the present invention. Atthe very least, and not as an attempt to limit the application of thedoctrine of equivalents to the scope of the claim, each numericalparameter should at least be construed in light of the number ofreported significant digits and by applying ordinary roundingtechniques.

One or more illustrative embodiments incorporating the inventionembodiments disclosed herein are presented herein. Not all features of aphysical implementation are described or shown in this application forthe sake of clarity. It is understood that in the development of aphysical embodiment incorporating the embodiments of the presentinvention, numerous implementation-specific decisions must be made toachieve the developer's goals, such as compliance with system-related,business-related, government-related and other constraints, which varyby implementation and from time to time. While a developer's effortsmight be time-consuming, such efforts would be, nevertheless, a routineundertaking for those of ordinary skill in the art and having benefit ofthis disclosure.

Therefore, the present invention is well adapted to attain the ends andadvantages mentioned as well as those that are inherent therein. Theparticular embodiments disclosed above are illustrative only, as thepresent invention may be modified and practiced in different butequivalent manners apparent to those skilled in the art having thebenefit of the teachings herein. Furthermore, no limitations areintended to the details of construction or design herein shown, otherthan as described in the claims below. It is therefore evident that theparticular illustrative embodiments disclosed above may be altered,combined, or modified and all such variations are considered within thescope of the present invention.

1. A method for producing a higher alcohol from a waste plasticfeedstock, comprising: (a) providing a hydrocarbon feed streamcomprising a pyrolysis oil feed obtained from pyrolysis of plasticwaste, wherein the pyrolysis oil comprises at least 20 wt % higherolefins with a carbon number in the range C5-C20, based on its totalhydrocarbon content; (b) contacting the hydrocarbon feed stream withsynthesis gas under hydroformylation conditions in the presence of ahydroformylation catalyst and recovering a hydroformylation product; (c)subjecting the hydroformylation product to hydrogenation and/or adistillation to recover a higher alcohol product.
 2. The method of claim1, wherein the hydrocarbon feed stream consists essentially of pyrolysisoil obtained from pyrolysis of plastic waste.
 3. The method of claim 1,wherein the hydrocarbon feed stream further comprises a higher olefinsconventional feed.
 4. The method of claim 3, wherein the higher olefinsconventional feed is a petroleum-based higher olefins feed, such as ahigher olefins feed obtained by oligomerization of C3=, C4=, C5=olefins.5. The method of claim 1, wherein the pyrolysis oil feed comprise atleast 50 wt % linear alpha-olefins, more preferably at least 60 wt %linear alpha-olefins, based on its total olefin content.
 6. The methodof claim 5, wherein the pyrolysis oil feed is characterized by anaverage number of branches per molecule that is less than 1, preferablyless than or equal to 0.8
 7. The method of claim 1, further comprising:prior to step (b), subjecting the pyrolysis oil feed to a distillationthereby separating one or more fractions corresponding to any narrow cutrange within the range C7-C20, in particular the carbon number rangesC7-C19, C7-C10, C7-C12, C10-C13, C13-C17, C13-C15 and C16-C19.
 8. Themethod of claim 1, further comprising: prior to step (b), subjecting atleast a portion of the hydrocarbon feed stream, preferably the pyrolysisoil feed, to a selective reduction of diolefins in the presence of anickel-containing catalyst.
 9. The method of claim 1, further comprisingprior to step (b), contacting at least a portion of the hydrocarbon feedstream, preferably the pyrolysis oil feed, with a water solution tothereby at least partially remove water-soluble contaminants.
 10. Themethod of claim 1, further comprising prior to step (b), contacting atleast a portion of the hydrocarbon feed stream, preferably the pyrolysisoil feed, with one or more adsorbents suitable to thereby at leastpartially remove one or more contaminants selected from: water, metals,chlorides, nitrogen-containing compounds, oxygenates, andphosphorous-containing compounds.
 11. A higher alcohol obtainable by themethod of claim
 1. 12. A composition comprising one or more derivativesof the higher alcohol of claim
 11. 13. The composition of claim 12,wherein the derivative comprises esters of dicarboxylic acids, esters ofpolycarboxylic acids, alkoxylated alcohols, sulfated alcohols, sulfatedalkoxylated alcohols and alcohol ether amines.
 14. The composition ofclaim 12 wherein the derivative comprises esters of the primary alcoholcomposition with one or more acids.
 15. The composition of claim 14,wherein the acids comprise one or more of phthalic acid, adipic acid,sebacic acid, lauric acid, myristic acid, palmitic acid, stearic acid,oleic acid, succinic acid and trimellitic acid.